Dyed artificial leather base material, napped artificial leather, resin layer-equipped artificial leather, shoes, decorating sheet, and decorative molded body

ABSTRACT

Disclosed is an artificial leather base material having a surface with a lightness L* value of ≤50 and including a fiber base material that includes cationic dye-dyeable polyester fibers and an elastic polymer, the artificial leather base material being dyed with at least one cationic dye. Also provided is a resin layer-equipped artificial leather, a napped artificial leather, and a shoe that use the artificial leather base material is used. Also provided is a decorating sheet including the artificial leather base material, and a decorative molded body using the same.

TECHNICAL FIELD

The present invention relates to a dyed artificial leather basematerial, a napped artificial leather, a resin layer-equipped artificialleather, a shoe, a decorating sheet, and a decorative molded body.

BACKGROUND ART

Artificial leather base materials are used for the surface members ofvarious articles for daily use. Specifically, an artificial leather basematerial can be used, for example, as the upper material of shoes bybeing integrated with an outsole made of a rubber, a synthetic resin orthe like, or as the surface member of a car seat, a general merchandiseor the like by being attached to a member made of a different materialwith an adhesive. When used as the surface member, the artificialleather base material is formed into a napped artificial leather byforming fiber naps on the surface thereof, or formed into a resinlayer-equipped artificial leather by integrating therewith a resin of afilm, a urethane foam, a hard plastic plate or the like, thus impartinga unique appearance design, tactile impression or texture to theartificial leather base material.

Decorative molded bodies for which an artificial leather is used as asurface decorating sheet are also known as the exterior member,including, for example, the casing of a mobile device such as a mobilephone, a home electrical appliance, and a sanitary product, the interiormember of a vehicle, a vessel, an aircraft and the like, and theexterior member of a building material, an article of furniture and thelike. For example, PTL 1 below discloses a decorating sheet, which is anartificial leather integrated with a resin molded body by in-molding,and a decorative molded body using the same.

In general, an artificial leather base material is produced by coloringa fiber base material including a non-woven fabric and an elasticpolymer such as polyurethane. As the fibers included in the artificialleather base material, polyester fibers can be preferably used becauseof the excellent heat resistance and moldability. As the dye for dyeingthe artificial leather base material including polyester fibers, adisperse dye is widely used because of the excellent color development.However, an artificial leather base material dyed with a disperse dye isproblematic in that the disperse dye may contaminate another member anda molded body to be decorated, and such contamination can be prominentwhen the ambient temperature or the pressure applied to the member ishigh, or when the adhesive or the like contains an organic solvent.

For example, PTL 2 below discloses an ultrafine fiber napped non-wovenfabric including polyester ultrafine fibers that can be dyed with acationic dye and an elastomeric matrix, and a UV stabilizer composition.Also, PTL 3 below discloses a technique relating to a synthetic leather,namely, a synthetic leather obtained by forming a resin layer on thesurface of a double-raschel knitted fabric. The double-raschel knittedfabric includes a front knitted fabric, a back knitted fabric, and apile layer connecting the front knitted fabric and the back knittedfabric. The fibers constituting the front knitted fabric are polyesterfibers dyed with a cationic dye, and a resin layer is formed on thefront knitted fabric side. Then, the polyester fibers include adicarboxylic acid component composed mainly of terephthalic acid, and apolyester including a glycol component composed mainly of ethyleneglycol, wherein the dicarboxylic acid component includes a componentrepresented by the following formula (III):

[In the formula (III), X represents a metal ion, a quaternaryphosphonium ion, or a quaternary ammonium ion.]

For example, PTL 4 below discloses a deodorizing fabric that has beensubjected to a deodorizing treatment, wherein the deodorizing fabricincludes, as a copolymer component, copolymerized polyester fibers acontaining, in an acid component, a metal salt (A) of a sulfoisophthalicacid or a quaternary phosphonium salt or a quaternary ammonium salt (B)of a sulfoisophthalic acid such that 3.0≤A+B≤5.0 (mol %) and0.2≤B/(A+B)≤0.7, and the deodorizing fabric has been dyed with acationic dye.

CITATION LIST Patent Literatures

[PTL 1] WO 2015/029453 pamphlet

[PTL 2] Japanese Laid-Open Patent Publication No. 2007-16378 [PTL 3]Japanese Laid-Open Patent Publication No. 2014-29050 [PTL 4] JapaneseLaid-Open Patent Publication No. 2010-242240 SUMMARY OF INVENTIONTechnical Problem

For a grain-finished artificial leather obtained by stacking a darkcolor resin layer on an artificial leather base material includingpolyester fibers, the color of the artificial leather base materialcovered by the resin layer is not visible from the surface side.Accordingly, there is no need to color the artificial leather basematerial. When a suede-like or nubuck-like napped artificial leatherdyed with a disperse dye is integrated with an outsole made of a rubberor a synthetic resin as a shoe upper material, constraints are imposedon the shoe design so that the contamination of the outsole caused tythe disperse dye migrating from the napped artificial leather is lessconspicuous, for example, by reducing the amount of the dye for dyeingthe napped artificial leather to achieve a light color, using a nappedartificial leather for which a pigment is used for coloring, or coloringthe outsole in a dark color.

However, in order to satisfy the customers' requirement for the designdiversification, there is a need for a resin layer-equipped artificialleather obtained by combining a dark-color artificial leather with awhite or light-color resin layer. There is also a need for a darkcolored napped artificial leather as a shoe upper material with which awhite or light-color outsole is to be combined. In such applications,the disperse dye may migrate from the artificial leather base materialto the white or light-color resin layer or the outsole, thuscontaminating these portions.

In the case of producing a decorative molded body by integrating, with amolded body to be decorated, a decorating sheet including an artificialleather base material dyed with a disperse dye, the following problemarises. The decorative molded body is produced, for example, by primarydecorative molding such as in-molding in which, in a state in which adecorating sheet or a preform molded body obtained by shaping thedecorating sheet into a three-dimensional shape is disposed in advancein a cavity of a mold, molten resin is injected into the cavity, andthen solidified, thus molding a decorative molded body in which thedecorating sheet is integrated with the surface of a resin molded body.As another method, the decorative molded body can be produced bysecondary decorative molding such as overlaying in which a decoratingsheet is integrated with a resin molded body by being attached to theresin molded body with an adhesive while shaped by heating so as tofollow the surface thereof. In the case of a decorating sheet dyed witha disperse dye, the dye may be sublimated by heat or pressure or may beliberated by an organic solvent contained in the adhesive, when thedecorating sheet is integrated with the molded body to be decorated. Asa result, the disperse dye that has migrated from the decorating sheetcontaminates the molded body to be decorated, which is a resin moldedbody. When the molded body to be decorated is white or light color, thecontamination caused by the disperse dye becomes even more conspicuous,thus significantly compromising the commercial value.

As described above, for a decorative molded body in which a resinlayer-equipped artificial leather whose resin layer has a dark color isintegrated with a resin molded body, the artificial leather basematerial is covered by the dark color resin layer, so that the color ofthe artificial leather base material is not visible from the surfaceside. However, depending on the shape of the decorative molded body, forexample, in the case of a decorative molded body having an opening, thecross section of the decorating sheet is exposed. Furthermore, when anafter treatment such as a skiving treatment is not performed on an endface of the decorating sheet at an end face of a decorative molded body,the cross section of the decorating sheet is also exposed. For adecorative molded body having such a shape in which the cross section ofthe decorating sheet is exposed, in order to prevent degradation of thedesign quality at the end face and the cross section of the opening,there is a need for a resin layer-equipped artificial leather obtainedby coloring an artificial leather base material, and, therefore, thereis the problem of contamination of the resin layer and the resin moldedbody caused by the disperse dye used for dying the artificial leatherbase material.

It is an object of the present invention to provide a dark coloredartificial leather base material, wherein the artificial leather basematerial is less likely to contaminate a resin layer or a resin moldedbody with a dye even when it comes into contact with another member suchas as e resin layer stacked on the artificial leather base material, ora resin molded body such as an outsole, and a product using the samethat has excellent design quality. It is another object of the presentinvention to provide a decorating sheet for use in production of adecorative molded body, wherein the decorating sheet uses a dark coloredartificial leather base material that is less likely to causecontamination of a molded body to be decorated, with which it comes intocontact, with a dye, and a decorative molded body using the decoratingsheet.

Solution to Problem

An aspect of the present invention is directed to an artificial leatherbase material including a fiber base material that includes cationicdye-dyeable polyester fibers and an elastic polymer, the artificialleather base material being dyed with at least one cationic dye andhaving a surface with a lightness L* value of ≤50. Such an artificialleather base material is less likely to cause migration of the dye toanother member in contact therewith even though it is colored in a darkcolor. In particular, even when such an artificial leather base materialis integrated with a white or light-color resin layer or resin moldedbody, the artificial leather base material is less likely to contaminatethe resin layer or the resin molded body. The fiber base materialincludes, for example, a non-woven fabric of cationic dye-dyeablepolyester fibers and an elastic polymer.

For example, it is preferable that the artificial leather base materialhas a grade of color difference, determined in an evaluation of colormigration to a white polyvinyl chloride film with a thickness of 0.8 mmunder a load of 750 g/cm² at 50° C. for 16 hours, of 4 or more, becauseeven a dark colored artificial leather base material is less likely tocontaminate a white or light-color resin layer, a resin molded body, oranother member in contact therewith. Note that that “a grade of colordifference, determined in an evaluation of color migration to a whitepolyvinyl chloride film, of 4 or more” means that color differenceΔE*≤2.0 is achieved in the evaluation of color migration.

In the artificial leather base material, it is preferable that, after awhite polyurethane film with a thickness of 250 μm is pressure-bondedunder heating to a surface of the artificial leather base material via apolyurethane adhesive under 5 Kg/cm² at 130° C. for 1 minute to form aresin layer-equipped artificial leather, and the resin layer-equippedartificial leather is pressurized under heating under 20 Kg/cm² at 150°C. for 1 minute, the artificial leather has a grade of color difference,determined in an evaluation of color migration to the white polyurethanefilm, of 3 or more. This is because even when a resin layer-equippedartificial leather including a white or light-color resin layer isformed, the artificial leather base material is less likely tocontaminate the resin layer. Note that “a grade of color difference,determined in an evaluation of color migration to the white polyurethanefilm, of 3 or more” means that a color difference ΔE* of ≤3.8 isachieved in the evaluation of color migration.

It is preferable that the artificial leather base material has a gradeof color difference, determined in an evaluation of color migrationusing methyl ethyl ketone (MEK), of 2 or more, because the artificialleather base material is less likely to be contaminate the resin layerwhen the artificial leather base material is bonded to a white orlight-color resin layer with an adhesive containing a solvent. Note that“a grade of color difference, determined in an evaluation of colormigration using methyl ethyl ketone (MEK), of 2 or more” means that agrade of color difference, determined in an evaluation of colormigration to a white polyurethane film in accordance with the JISgray-scale standard, of 2 or more.

In the artificial leather base material, it is preferable that a productof a softness and a thickness of the artificial leather base material is2 or more, because a flexible texture can be achieved.

It is preferable that the artificial leather base material contains 0.5to 20 parts by mass of the cationic dye, per 100 parts by mass of thefiber base material, because even a dark colored artificial leather basematerial is less likely to cause migration of the dye.

It is preferable that the artificial leather base material has a grade,determined in a water fastness test for a cotton cloth in accordancewith JIS L 0846, of 4-5 or more, because the migration of the dye issufficiently suppressed since the cationic dye that is not ionicallybonded, which is likely to be detached by coming into contact withwater, has been removed.

Another aspect of the present invention is directed to a resinlayer-equipped artificial leather including: any one of theabove-described artificial leather base materials; and a resin layerstacked on at least one surface of the artificial leather base material.Preferably, the resin layer has a surface with a lightness L* value of>50.

In the resin layer-equipped artificial leather, it is preferable that alightness difference ΔL* between the artificial leather base materialand the resin layer is 10 or more, because a high-contrast end face orappearance with a color difference and excellent design quality can beobtained, and the effects of the present invention become prominent.

Another aspect of the present invention is directed to a nappedartificial leather obtained by napping at least one surface of any oneof the above-described artificial leather base materials, the artificialleather base material having a surface with a lightness L* value of ≤50.

Another aspect of the present invention is directed to a shoe including:the above-described napped artificial leather as an upper material; andan outsole bonded to the upper material, the outsole having a lightnessL* value of >50.

Another aspect of the present invention is directed to a decoratingsheet for being integrated with a molded body to be decorated, includingany one of the above-described artificial leather base materials. Withsuch a decorating sheet, the contamination of the molded body to bedecorated with a dye can be suppressed during the manufacturing processvia a heating step of a decorative molded body or in use thereof.

Preferably, the decorating sheet is a preform molded body shaped into athree-dimensional shape. With such a preform molded body, the migrationof the dye to another member can also be suppressed in preform molding.

Another aspect of the present invention is directed to a decorativemolded body including: a molded body to be decorated; and the decoratingsheet as described above that is stacked and integrated on the moldedbody to be decorated. Such a decorative molded body is less likely to becontaminated by the dye migrating from the artificial leather basematerial even when the molded body to be decorated is white or lightcolored, or transparent, such as a molded body to be decorated having alightness L* value of >50. In particular, this is also preferable whenthe molded body to be decorated has a lightness L* value of >50, such asa white, light-color, or transparent one, or when the lightnessdifference ΔL* between the molded body to be decorated and thedecorating sheet is 10 or more, because the contamination by the dye isless conspicuous.

Advantageous Effects of Invention

According to the present invention, it is possible to obtain anartificial leather base material dyed in a dark color that is lesslikely to cause contamination of a resin layer or a resin molded bodywith a dye even when it is integrated with a white or light-colorsurface resin layer or a resin molded body such as an outsole, and anartificial leather product including the artificial leather basematerial. Furthermore, according to the present invention, it ispossible to obtain a decorating sheet including an artificial leatherbase material dyed in a dark color that is less likely to causecontamination of a molded body to be decorated with a dye, and adecorative molded body, such as a casing, using the same.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross-sectional view of a resin layer-equippedartificial leather 10 including an artificial leather base material 1according to an embodiment.

FIG. 2A is a schematic diagram of a shoe 20 that uses the artificialleather base material 1 according to the embodiment as an uppermaterial.

FIG. 2B is a schematic cross-sectional view of the shoe 20.

FIG. 3A is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using a decorating sheet 11including the artificial leather base material.

FIG. 3B is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using the decorating sheet 11including the artificial leather base material.

FIG. 3C is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using the decorating sheet 11including the artificial leather base material.

FIG. 3D is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using the decorating sheet 11including the artificial leather base material.

FIG. 3E is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using the decorating sheet 11including the artificial leather base material.

FIG. 3F is an explanatory diagram for illustrating a step for molding apreform molded body 15 by vacuum molding using the decorating sheet 11including the artificial leather base material.

FIG. 4A is an explanatory diagram for illustrating a step for molding adecorative molded body 30 by in-molding using the preform molded body15.

FIG. 4B is an explanatory diagram for illustrating a step for molding adecorative molded body 30 by in-molding using the preform molded body15.

FIG. 4C is an explanatory diagram for illustrating a step for moldingthe decorative molded body 30 by in-molding using the preform moldedbody 15.

FIG. 4D is an explanatory diagram for illustrating a step for moldingthe decorative molded body 30 by in-molding using the preform moldedbody 15.

FIG. 5 is a schematic cross-sectional view of a decorative molded body50 produced by bonding a resin layer-equipped artificial leather 40 to amolded body 43 to be decorated.

FIG. 6 is a schematic perspective view showing the shape and thedimensions of a preform molded body according to examples.

DESCRIPTION OF EMBODIMENTS

First, an embodiment of an artificial leather base material according tothe present invention will be described in detail, in conjunction withan exemplary production method thereof. Note that the artificial leatherbase material may be used as a resin layer-equipped artificial leatherby forming a resin layer on the surface thereof, may be used as a nappedartificial leather formed by napping the surface thereof into asuede-like or nubuck-like surface, or may be directly used as anartificial leather.

In the production method of an artificial leather base materialaccording to the present embodiment, first, a fiber base material thatincludes a fiber fabric including cationic dye-dyeable polyester fibersand an elastic polymer applied to the fiber fabric is prepared. The“cationic dye-dyeable polyester fibers” refer to polyester fibers, aswill be described below, that include dye sites for a cationic dye inthe molecule.

The fineness of the dyeable polyester fibers is not particularlylimited. For example, it is possible to use regular fibers having afineness of 1 dtex or more, or ultrafine fibers having a fineness ofless than 1 dtex. From the viewpoint of particularly suppressing themigration of the cationic dye to another member, the fineness ispreferably 0.05 to 5 dtex, more preferably 0.09 to 4 dtex, particularlypreferably 0.1 to 3 dtex, quite particularly preferably 0.14 to 2.5dtex. With such a fineness, good color development can also be achievedwith a small amount of the cationic dye, so that the migration of thecationic dye can be suppressed, and the flexible texture can bemaintained. When the fineness is too low, the surface area of the fibersbecomes too large, so that it becomes difficult to develop a dark colorunless the cationic dye is used at a high concentration. As a result,the cationic dye tends to migrate to another member. When the finenessis too high, the surface area of the fibers becomes small. Accordingly,dyeing can be achieved with a smaller dye content in the case ofdeveloping the same color, so that the dye is less likely to migrate. Onthe other hand, in the case of achieving a napped finish, the writingeffect and the napped feel are reduced, the texture tends to be hard,and the appearance and the surface touch are degraded. For use as adecorating sheet, a fineness that is too high tends to result in reducedstretchability during softening by heating, thus making it difficult toshape an accurate shape during molding.

As the fiber fabric, it is possible to use a non-woven fabric, a wovenfabric, a knitted fabric, and the like without any particularlimitation. Among these, a non-woven fabric, in particular, an entanglednon-woven fabric obtained by entangling ultrafine fibers are preferable.The non-woven fabric obtained by entangling ultrafine fibers can beeasily stretched during molding. In the case of producing a decorativemolded body by in-molding, which will be described below, the non-wovenfabric makes it difficult for molten resin to permeate the artificialleather base material, thus retaining a high fiber-like texture. In thepresent embodiment, a method for producing, as an example of the fiberfabric, an entangled non-woven fabric (hereinafter also simply referredto as a “non-woven fabric”) obtained by entangling ultrafine fibers ofcationic dye-dyeable polyester fibers through an entangling treatment ofultrafine fiber-generating fibers will be described in detail as arepresentative example. Note that the type of the non-woven fabricobtained by entangling ultrafine fibers is not particularly limited, anda non-woven fabric that uses direct spun ultrafine fibers may be used.

In the production of an entangled non-woven fabric made of ultrafinefibers of a cationic dye-dyeable polyester, first, an entanglednon-woven fabric of ultrafine fiber-generating fibers is produced.Examples of the production method of the entangled non-woven fabric ofultrafine fiber-generating fibers include a method involvingmelt-spinning ultrafine fiber-generating fibers and directly collectingthe resultant fibers as long fibers without intentionally cutting them,thus forming a fiber web, and a method involving forming a fiber web bycarding or the like using staples obtained by cutting ultrafinefiber-generating fibers into a predetermined length, and thereaftersubjecting them to a known entangling treatment. Note that “long fibers”refer to fibers that are continuous in the length direction other thanstaples, and are also referred to as “filaments”. From the viewpoint ofsufficiently increasing the fiber density, the length of the long fibersis, for example, preferably 100 mm or more, more preferably 200 mm ormore. The upper limit of the length of the long fibers is notparticularly limited, and may be several meters, several hundred meters,several kilometers or longer, and be continuously spun. In the presentembodiment, the production of a long fiber-web will be described indetail as a representative example.

“Ultrafine fiber-generating fibers” refer to fibers that generateultrafine fibers having a small fineness as a result of performing achemical or physical post-treatment on the spun fibers. In the presentembodiment, a production method using island-in-the-sea composite fibersas the ultrafine fiber-generating fibers will be described; however,known ultrafine fiber-generating fibers such as strip/division-typecomposite fibers may be used in place of the island-in-the-sea compositefibers.

An island-in-the-sea composite fiber is a multicomponent composite fibercomposed of at least two polymers, and has a cross section on which anisland component polymer is dispersed in a matrix composed of a seacomponent polymer. A long-fiber web of the island-in-the-sea compositefibers is formed by melt-spinning the island-in-the-sea composite fibersand directly collecting the resultant fibers as long fibers on a netwithout cutting them.

In the present embodiment, it is preferable to use, as the islandcomponent polymer, a cationic dye-dyeable polyester obtained bycopolymerization of a copolymerizable monomer including a dicarboxylicacid component composed mainly of terephthalic acid and including 1.5 to3 mol % of a component represented by the following formula (I), and aglycol component composed mainly of ethylene glycol.

[In the above formula (I), R represents hydrogen, or an alkyl group or a2-hydroxyethyl group having 1 to 10 carbon atoms, and X represents ametal ion, a quaternary phosphonium ion, or a quaternary ammonium ion.]

Examples of the compound represented by the formula (I) include: alkalimetal salts (lithium salt, sodium salt, potassium salt, rubidium salt,and cesium salt) of 5-sulfoisophthalic acid; 5-tetraalkyl phosphoniumsulfoisophthalic acid such as 5-tetrabutyl phosphonium sulfoisophthalicacid, and 5-ethyl tributyl phosphonium sulfoisophthalic acid; and5-tetraalkyl ammonium sulfoisophthalic acid such as 5-tetrabutylammonium sulfoisophthalic acid and 5-ethyl tributyl ammoniumsulfoisophthalic acid. The compounds represented by the formula (I) maybe used alone or in a combination of two or more. Among these, it ispreferable to include a compound represented by the formula (I) where Xis a quaternary phosphonium ion or a quaternary ammonium ion, because acationic dye-dyeable polyester having excellent mechanical propertiesand high-speed spinnability can be obtained. It is preferable to use acationic dye-dyeable polyester obtained by polymerization of acopolymerizable monomer that includes a dicarboxylic acid componentincluding 1.5 to 3 mol % of the compound represented by the formula (I),in particular, the compound represented by the formula (I) where X is aquaternary phosphonium ion or a quaternary ammonium ion and composedmainly of terephthalic acid, and a glycol component composed mainly ofethylene glycol, because color migration can be easily suppressed evenwhen the artificial leather base material is dyed in a dark a color.

The ratio of the unit in the cationic dye-dyeable polyester derived fromthe formula (I) that is represented by the following formula (II):

[In the above formula (II), X represents a metal ion, a quaternaryphosphonium ion, or a quaternary ammonium ion.] is preferably 1.5 to 3mol %, more preferably 1.6 to 2.5 mol %.

When the ratio of the unit represented by the formula (II) is less than1.5 mol %, the dyeing fastness when the artificial leather base materialis dyed with a cationic dye tends to be reduced. On the other hand, whenthe ratio of the unit represented by the formula (II) exceeds 3 mol %,the high-speed spinnability is reduced, thus making it difficult toobtain ultrafine fibers. Also, the mechanical properties, such as tearstrength, of the resulting artificial leather base material tend to besignificantly reduced.

Here, “mainly composed of terephthalic acid” means terephthalic acidconstitutes 50 mol % or more of the dicarboxylic acid component in thecopolymerizable monomer. The terephthalic acid content of thedicarboxylic acid component is preferably 75 mol % or more. For thepurpose of improving the dyeing fastness of a cationic dye, increasingthe high-speed spinnability, and improving the shaping properties whenusing the artificial leather base material for molding applications,another dicarboxylic acid, excluding the compound represented by theformula (I), may be included as the dicarboxylic acid component in orderto lower the glass transition temperature. Specific examples of anotherdicarboxylic acid component may include other dicarboxylic acids,including, for example, aromatic dicarboxylic acid such as isophthalicacid, cyclohexane dicarboxylic acid such as 1,4-cyclohexane dicarboxylicacid, and aliphatic dicarboxylic acid such as adipic acid, andderivatives thereof. Among these, it is particularly preferable to useisophthalic acid, or a combination of 1,4-cyclohexane dicarboxylic acidand adipic acid, or derivatives thereof, because of the excellentmechanical properties and high-speed spinnability.

As the dicarboxylic acid component, the copolymerization ratio ofanother dicarboxylic acid is preferably 2 to 12 mol %, more preferably 3to 10 mol %. When the copolymerization ratio of another dicarboxylicacid is less than 2 mol %, the glass transition temperature is notsufficiently lowered, and the degree of orientation of amorphous sitesinside the fibers increases, so that dyeability tends to be reduced. Onthe other hand, when the copolymerization ratio of another dicarboxylicacid exceeds 12 mol %, the glass transition temperature is excessivelylowered, and the degree of orientation of the amorphous sites inside thefibers is reduced, so that the fiber strength tends to be reduced. Notethat when an isophthalic acid unit is contained as another dicarboxylicacid unit, it is preferable to contain, as the dicarboxylic acid unit,preferably 1 to 6 mol %, more preferably 2 to 5 mol % of the isophthalicacid unit, because of the excellent mechanical properties and high-speedspinnability. When a 1,4-cyclohexane dicarboxylic acid unit and anadipic acid unit are contained, it is preferable to include, preferably1 to 6 mol %, more preferably 2 to 5 mol % of each of the1,4-cyclohexane dicarboxylic acid unit and the adipic acid unit, becausea cationic dye-dyeable polyester having excellent mechanical propertiesand high-speed spinnability can be obtained.

“Composed mainly of ethylene glycol” means that ethylene glycolconstitutes 50 mol % or more of the glycol component of thecopolymerizable monomer. The ethylene glycol content of the glycolcomponent is preferably 75 mol % or more, more preferably 90 mol % ormore. Examples of other components include diethylene glycol andpolyethylene glycol.

The glass transition temperature (Tg) of the cationic dye-dyeablepolyester is not particularly limited, and is preferably 60 to 70° C.,more preferably 60 to 65° C. When Tg is too high, the high-speedstretchability is reduced, and the shaping properties tend to be reducedwhen heat-molding the artificial leather base material for use.

If necessary, a colorant such as carbon black, a weathering agent, anantifungal agent, and the like may be added to the cationic dye-dyeablepolyester, so long as the effects of the present invention are notimpaired.

As the sea component polymer, a polymer having higher solubility in asolvent or higher decomposability by a decomposition agent than those ofthe cationic dye-dyeable polyester is selected. Specific examples of thesea component polymer include a water-soluble polyvinyl alcohol resin(water-soluble PVA), polyethylene, polypropylene, polystyrene, anethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, astyrene-ethylene copolymer, and a styrene-acrylic copolymer.

The island-in-the-sea composite fibers can be produced by melt spinningin which the sea component polymer and the cationic dye-dyeablepolyester serving as the island component polymer are melt-extruded froma multicomponent fiber spinning spinneret. The fineness of theisland-in-the-sea composite fibers is not particularly limited, and ispreferably 0.5 to 10 dtex, more preferably 0.7 to 5 dtex.

The molten island-in-the-sea composite fibers discharged from thespinneret are cooled by a cooling apparatus, and are further drawn outand attenuated by a suction apparatus such as an air jet nozzle so as tohave a desired fineness. Then, the drawn and attenuated long fibers arepiled on a collection surface of a movable net or the like, therebyobtaining a long-fiber web. Note that, in order to stabilize the shape,a part of the long-fiber web may be further pressure-bonded by pressingthe long-fiber web if necessary.

The obtained long-fiber web is subjected to an entangling treatment,thereby producing an entangled non-woven fabric of long fibers. Specificexamples of the entangling treatment for the long-fiber web include atreatment in which a plurality of layers of long-fiber webs aresuperposed in the thickness direction by using a cross lapper or thelike, and subsequently needle-punched simultaneously or alternately fromboth sides such that at least one barb penetrates the web.

In addition, an oil solution, an antistatic agent, or the like may beadded to the long fiber-web in any stage from the spinning step to theentangling treatment of the island-in-the-sea composite fiber.Furthermore, if necessary, the fiber density of the long fiber-web maybe further increased in advance by performing a shrinking treatment inwhich the long-fiber web is immersed in hot water at about 70 to 150°C., thus imparting uniformity. The fiber density may be furtherincreased by performing hot pressing after the entangling treatment soas to impart shape stability. The basis weight of the entanglednon-woven fabric is preferably in the range of about 100 to 2000 g/m².

If necessary, a treatment to further increase the fiber density and thedegree of entanglement may be performed by heat-shrinking the entanglednon-woven fabric of the island-in-the-sea composite fibers. A furtherdensification of and the fixation of the shape of the entanglednon-woven fabric, and the smoothing of the surface thereof may beperformed by further hot-pressing the heat shrunk entangled non-wovenfabric.

By removing the sea component polymer from the island-in-the-seacomposite fibers in the entangled non-woven fabric, an entanglednon-woven fabric composed of ultrafine fibers of the cationicdye-dyeable polyester is obtained. As the method for removing the seacomponent polymer, a conventionally known ultrafine fiber formationmethod such as a method involving immersing the entangled non-wovenfabric in a solvent or decomposition agent capable of selectivelyremoving only the sea component polymer can be used without anyparticular limitation. For example, in the case of using thewater-soluble PVA as the sea component polymer, it is preferable to usehot water as the solvent.

In the case of using the water-soluble PVA as the sea component polymer,it is preferable to remove the water-soluble PVA by extraction until theremoval rate of the water-soluble PVA becomes about 95 to 100% byimmersing the web in hot water at 85 to 100° C. for 100 to 600 seconds.Note that the water-soluble PVA can be more efficiently removed byextraction by repeating a dip-nipping treatment in the immersing.

The basis weight of the entangled non-woven fabric composed of ultrafinefibers of the cationic dye-dyeable polyester thus obtained is preferably140 to 3000 g/m², more preferably 200 to 2000 g/m².

In the production of the artificial leather base material, an elasticpolymer such as polyurethane is impregnated into the internal voids ofthe entangled non-woven fabric before or after, or both before and aftergenerating ultrafine fibers from ultrafine fiber-generating fibers suchas island-in-the-sea composite fibers in order to impart shape stabilityand fullness to the entangled non-woven fabric of the cationicdye-dyeable polyester.

Specific examples of the elastic polymer include polyurethanes,acrylonitrile elastomers, olefin elastomers, polyester elastomers,polyamide elastomers, and acrylic elastomers. Among these, polyurethanesare preferable.

Note that the elastic polymer may further contain a colorant such as apigment (e.g., carbon black) or a dye, a coagulation regulator, anantioxidant, an ultraviolet absorber, a fluorescent agent, an antifungalagent, a penetrant, an antifoaming agent, a lubricant, a water-repellentagent, an oil-repellent agent, a thickener, a filler, a curingaccelerator, a foaming agent, a water-soluble polymer compound such aspolyvinyl alcohol or carboxymethyl cellulose, inorganic fine particles,and a conductive agent, so long as the effects of the present inventionare not impaired.

The content ratio of the elastic polymer is preferably 0.1 to 50 mass %,more preferably 3 to 40 mass %, particularly preferably 5 to 25 mass %,quite particularly preferably 10 to 15 mass %, relative to the totalamount of the elastic polymer and the cationic dye-dyeable polyesterfibers, because color migration to the resin layer in contact with theartificial leather base material dyed with a cationic dye, the moldedbody to be decorated and other members is less likely to occur, and anartificial leather base material having well-balanced fullness andsuppleness or the like can be obtained.

Thus, a raw fabric of the fiber base material, which is an entanglednon-woven fabric of the cationic dye-dyeable polyester that has beenimpregnated with the elastic polymer is obtained. The raw fabric of thefiber base material is finished by being sliced into a plurality ofpieces in a direction perpendicular to the thickness direction or groundas needed so as to adjust the thickness. If necessary, the raw fabricmay be finished into a napped fiber base material that has been nappedby being buffed on at least on one surface by using sand paper or emerypaper with a grit number of preferably about 120 to 600, more preferablyabout 320 to 600. The napped fiber base material becomes a suede-like ornubuck-like artificial leather.

Then, the fiber base material is dyed with a cationic dye, therebyobtaining an artificial leather base material dyed with a cationic dye.By dyeing the fiber base material with a cationic dye, excellent dyeingfastness is exerted as a result of the cationic dye being fixed by ionicbonding to the sulfonium ions that serve as the dye sites of thecationic dye of the cationic dye-dyeable polyester and are contained inthe unit represented by the following formula (I_(a)):

As the cationic dye, any conventionally known cationic dye may be usedwithout any particular limitation. Note that the cationic dye isdissolved in a dye liquid to become a dye ion exhibiting cationicproperties, for example, a dye ion including a quaternary ammonium groupor the like, and is conically bonded to the cationic dye-dyeablepolyester fibers. In general, such a cationic dye forms a salt with ananion such as a chlorine ion. This anion such as a chlorine ion iscontained in the cationic dye, but will be washed off by washingperformed after dyeing. Specific examples of the cationic dye include:azo-based blue cationic dyes such as a C.I. Basic Blue 54 and C.I. BasicBlue 159; oxazine-based blue cationic dyes such as C.I. Basic Blue 3,C.I. Basic Blue 6, C.I. Basic Blue 10, C.I. Basic Blue 12, C.I. BasicBlue 75, and C.I. Basic Blue 96; coumarin-based dyes such as C.I. BasicYellow 40; methine-based dyes such as C.I. Basic Yellow 21;azomethine-based dyes such as C.I. Basic Yellow 28; azo-based red dyessuch as C.I. Basic Red 29 and C.I. Basic Red 46; and xanthene-based dyessuch as C.I. Basic Violet 11. These may be used alone or in acombination of two or more.

The dyeing method is not particularly limited, and examples thereofinclude methods in which dyeing is performed using a dyeing machine suchas a jet dyeing machine, a beam dyeing machine, or a jigger. As for theconditions for dyeing processing, dyeing may be performed at a highpressure, but it is preferable to perform dyeing at normal pressure,because the environmental load is low, and the dyeing cost can bereduced. In the case of performing dyeing at normal pressure, the dyeingtemperature is preferably 60 to 100° C., more preferably 80 to 100° C.During dyeing, a dyeing assistant such as acetic acid or mirabilite maybe used.

In the case of dyeing the fiber base material with a cationic dye, theconcentration of the cationic dye in a dye liquid is in the range ofpreferably 0.05 to 20% owf, more preferably 0.1 to 15% owf, particularlypreferably 0.5 to 20% owf, quite particularly preferably 1.0 to 15% owf,relative to the fiber base material to be dyed, because the color of thecationic dye-dyeable polyester fibers is sufficiently developed in adark color, and the cationic dye becomes less likely to migrate to othermembers. When the concentration of the cationic dye in the dye liquid istoo high, a large amount of the cationic dye that is not fixed to thedye sites of the cationic dye-dyeable polyester fibers is contained, sothat the cationic dye tends to migrate to other members. When theconcentration of the cationic dye is too low, it tends to be difficultto color the fiber base material in a dark color such as a color with alightness L* value of ≤50.

It is preferable that the fiber base material dyed with a cationic dyeis subjected to a washing treatment in a hot water bath containing ananionic surfactant, thereby removing a cationic dye having a low bondingstrength. With such a washing treatment, the cationic dye having a lowbonding strength is sufficiently removed, and other members such as aresin layer that is stacked and a molded body to be decorated are lesslikely to be contaminated with the cationic dye contained in theartificial leather base material. Specific examples of the anionicsurfactant include Sordine R manufactured by NISSEI KASEI CO. LTD.,SENKANOL A-900 manufactured by SENKA corporation, and Meisanol KHMmanufactured by Meisei Chemical Works, Ltd.

The washing treatment in the hot water bath containing an anionicsurfactant is performed in a hot water bath at preferably 50 to 100° C.,more preferably 60 to 80° C. As the bath for the hot water bath, it ispreferable to use the dyeing machine with which the dyeing treatment hasbeen performed, because the production process can be simplified. Thewashing is performed for preferably about 10 to 30 minutes, morepreferably about 15 to 20 minutes. Also, the washing is repeated once ormore, preferably twice or more. The fiber base material dyed with acationic dye is dried after being washed.

The fiber base material dyed with a cationic dye may be furthersubjected to various finishing treatments as needed. Examples of thefinishing treatment include a flexibilizing treatment by crumpling, areverse seal brushing treatment, an antifouling treatment, ahydrophilization treatment, a lubricant treatment, a softener treatment,an antioxidant treatment, an ultraviolet absorber treatment, afluorescent agent treatment, and a flame retardant treatment. Thus, anartificial leather base material dyed with a cationic dye is obtained.

It is preferable that the fiber base material dyed with a cationic dyeis sufficiently washed by the above-described washing such that thewashable chlorine in the cationic dye is about 90 ppm or less, relativeto the weight of the resulting artificial leather base material, becausethe cationic dye becomes less likely to migrate to other members. Theartificial leather base material dyed with a cationic dye containspreferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts bymass, particularly preferably 0.5 to 10 parts by mass, quiteparticularly preferably 1.0 to 10 parts by mass of the cationic dye, per100 parts by mass of the fiber base material. When the cationic dyecontent per 100 parts by mass of the fiber base material is too large,the amount of the dye that is not bonded to the dye sites of thecationic dye-dyeable polyester fibers increases, so that the cationicdye tends to be likely to migrate to other members. On the other hand,when the cationic dye content is too small, it becomes difficult tocolor the fiber base material in preferably a dark color with alightness L* value of ≤50, more preferably a dark color with an L* valueof ≤35.

Preferably, the artificial leather base material dyed with a cationicdye according to the present embodiment has the following properties.Specifically, it is preferable that the cotton stain in a water fastnesstest in accordance with a JIS method (JIS L 0846) is determined to begrade 4-5 or more. When the cotton stain of the artificial leather basematerial in the water fastness test is determined to be grade 4-5 ormore, the artificial leather base material contains a small amount ofthe cationic dye that is not conically bonded, which is likely to bedetached by coming into contact with water, so that the cationic dye isinhibited from migrating to other members.

The artificial leather base material dyed with a cationic dye accordingto the present embodiment has a grade of color difference, determined inan evaluation of color migration to a white polyvinyl chloride film witha thickness of 0.8 mm under a load of 750 g/cm² at 50° C. for 16 hours,of preferably 4 or more, more preferably 5 or more. Furthermore, in theartificial leather base material dyed with a cationic dye according tothe present embodiment, when a white polyurethane film with a thicknessof 250 μm is pressure-bonded under heating to a surface of theartificial leather base material via a polyurethane adhesive under 5Kg/cm² at 130° C. for 1 minute to form a resin layer-equipped artificialleather, and the resin layer-equipped artificial leather is pressurizedunder heating under 20 Kg/cm² at 150° C. for 1 minute, the artificialleather has a grade of color difference of the white polyurethane film,of preferably 3 or more, more preferably 4 or more. With such anartificial leather base material, it is possible to achieve high dyeingfastness that makes the cationic dye less likely to migrate to othermembers.

Furthermore, the artificial leather base material dyed with a cationicdye according to the present embodiment has a grade of color difference,determined in an evaluation of color migration using methyl ethyl ketone(MEK), of preferably 2 or more, more preferably 3 or more, because thecationic dye is less likely to be isolated when it comes into contactwith a solvent, so that high dyeing fastness that makes the cationic dyeless likely to contaminate other members even in an application in whichthe artificial leather base material is integrated with a resin layerusing an adhesive or the like.

The thickness of the artificial leather base material dyed with acationic dye is not particularly limited, and is preferably 0.2 to 4 mm,more preferably 0.3 to 1.8 mm, because a flexible texture can beachieved. The softness of the artificial leather base material, which ismeasured in the manner described below, is preferably 2.0 to 6.0 mm,more preferably 2.5 to 5.0 mm, because a flexible texture can beachieved. The product of the softness and the thickness is preferably 2or more, more preferably 2.5 or more, because well-balanced thicknessand texture can be achieved, resulting in an elegant texture suitablefor an artificial leather product. The apparent density of theartificial leather base material is preferably 0.3 to 0.6 g/cm³ or more,particularly preferably 0.45 to 0.55 g/cm³ or more, because a flexibletexture can be achieved.

The artificial leather base material dyed with a cationic dye accordingto the present embodiment is less likely to cause contamination of theresin layer and a molded body to be decorated, which will be describedbelow, with a cationic dye even when the artificial leather basematerial is colored in a dark color such as a color with an L* value of50. Although the artificial leather base material dyed with a cationicdye has an L* value of ≤50, the effects of the present invention becomeprominent particularly when the artificial leather base material iscolored in a dark color such as a color with an L* value of ≤35. Notethat for an L* value of ≤35, the cationic dye-dyeable polyester fibersand the elastic polymer may be colored with a pigment such as carbonblack, in addition to being dyed with a cationic dye so as to have an L*value of ≤35. With such an artificial leather base material, even whenit is dark colored, it is possible to sufficiently inhibit the cationicdye from contaminating other member by using the above-describedcationic dye-dyeable polyester fibers, and performing a washingtreatment in a hot water bath containing an anionic surfactant, therebyadjusting the content of the cationic dye to the above-describedcontent.

The artificial leather base material dyed with a cationic dye accordingto the present embodiment described thus may be finished into asuede-like or nubuck-like napped artificial leather by napping thefibers on the surface thereof, or may be finished into a resinlayer-equipped artificial leather by providing a resin layer on thesurface thereof. Alternatively, the artificial leather base material maybe used as an artificial leather product such as shoes for which theartificial leather base material is integrated with a resin molded bodysuch as an outsole, or may be used as a decorating sheet that is to beintegrated with a molded body to be decorated used for production of adecorative molded body such as a casing of a mobile device. An exampleof such applications will be specifically described in detail below.

First, a description will be given of a resin layer-equipped artificialleather in which a resin layer is stacked and integrated on at least onesurface of an artificial leather base material dyed with a cationic dye.

FIG. 1 is a schematic cross-sectional view of a resin layer-equippedartificial leather 10 including an artificial leather base material 1.The resin layer-equipped artificial leather 10 includes an artificialleather base material 1, and a resin layer 2 stacked on one surface ofthe artificial leather base material 1. The artificial leather basematerial 1 is an artificial leather base material as described abovethat includes a surface with a lightness L* value of ≤50, and a fiberbase material including cationic dye-dyeable polyester fibers and anelastic polymer, the artificial leather base material 1 being dyed withat least one cationic dye. Examples of the resin layer 2 include layersthat have been used for forming the resin layers of the conventionallyknown resin layer-equipped artificial leathers, namely, layers composedmainly of polyurethane, an acrylonitrile elastomer, an olefin elastomer,a polyester elastomer, a polyamide elastomer, an acrylic elastomer orthe like.

In such a resin layer-equipped artificial leather 10, even when a whiteor light-color resin layer 2 such as the one having an L* value of >50,preferably an L* value>70, is formed, the resin layer 2 is less likelyto be contaminated by the cationic dye included in the artificialleather base material 1. For the resin layer-equipped artificial leather10, the lightness difference ΔL* in L* value between the artificialleather base material 1 and the resin layer 2 is preferably 10 or more,more preferably 20 or more, particularly preferably 30 or more, becausea high-contrast appearance having an excellent design quality can beachieved.

FIG. 2A is a schematic diagram showing the appearance of an upperportion of a shoe 20 that uses the artificial leather base material 1 asan upper material. FIG. 2B is a schematic cross-sectional view of theupper portion of the shoe 20. As shown in FIG. 2B, in the shoe 20, endportions of the artificial leather base material 1 are bonded to andintegrated with a rubber sole 3 made of a rubber, which is a light-colorresin layer with an L* value of >50, with adhesive layers 3 a, to form aresin layer-equipped artificial leather 7. A patch 5, which is alight-color resin layer with an L* value of >50, is bonded to thesurface of the artificial leather base material 1 with an adhesive layer5 a, to form a resin layer-equipped artificial leather 8.

The resin layer-equipped artificial leather 7 refers to a region havinga structure that includes the artificial leather base material 1 dyedwith a cationic dye that has a lightness L* value of ≤50, thelight-color or white rubber sole 3 made of a rubber that has an L* valueof >50 and is integrated with the end portions of the artificial leatherbase material 1 with the adhesive layers 3 a. The resin layer-equippedartificial leather 8 refers to a region including the artificial leatherbase material 1, and the patch 5, which is a light-color or white resinlayer that has an L* value of >50 and is bonded to and integrated withthe surface of the artificial leather base material 1 with the adhesivelayer 5 a. Such resin layer-equipped artificial leathers 7 and 8, evenwhen they are bonded to and integrated with the white or light-colorrubber sole 3 or patch 5, such as those having an L* value of >50,preferably an L* value>70, the cationic dye included in the dark-colorartificial leather base material 1 is less likely to contaminate therubber sole 3 and the patch 5. For such resin layer-equipped artificialleathers 7 and 8, ΔL*, which is a difference in L* value between theartificial leather base material 1 and the rubber sole 3 or the patch 5,is preferably 10 or more, more preferably 20 or more, particularlypreferably 30 or more, because of the excellent design quality due to acolor with an excellent contrast.

Next, a description will be given of a method for producing a decorativemolded body having a three-dimensional shape by integrating, with thesurface of a molded body to be decorated, a decorating sheet includingan artificial leather base material dyed with a cationic dye. In theproduction method of the decorative molded body according to the presentembodiment, a preform molded body obtained by molding a decorating sheetinto a three-dimensional shape by preform molding is produced inadvance.

First, a method for molding a preform molded body using vacuum moldingwill be described in detail with reference to FIGS. 3A to 3F. Note thata molding method such as vacuum pressure molding, pressure molding, orhot-press molding may be used in place of vacuum molding.

As shown in FIG. 3A, a non-air-permeable thermoplastic resin sheet 12 isplaced on a decorating sheet 11, which is a napped artificial leatherincluding an artificial leather base material dyed with a cationic dye,to form a superposed body 13. The decorating sheet 11, which is a nappedartificial leather, is air-permeable, and thus cannot be directlysubjected to vacuum molding. In the present embodiment, thethermoplastic resin sheet 12 is placed on the decorating sheet 11 inorder to temporarily impart airtightness to the decorating sheet 11 invacuum molding.

As the thermoplastic resin sheet, it is possible to use any sheet orfilm that is softened by heating during vacuum molding so as to beprovided with a shape, is capable of maintaining airtightness without apinhole or the like, and can be selectively detached in a later step,without any particular limitation. Examples of the thermoplastic resinfor fouling such a thermoplastic resin sheet include amorphousthermoplastic resins such as a (meth)acrylic resin, and crystallinethermoplastic resins having a low melting point, including, for example,polyolefin resins such as polyethylene and polypropylene. The thicknessof the thermoplastic resin sheet is preferably about 10 to 300 μm, morepreferably about 15 to 200 μm, particularly preferably about 30 to 100μm. When the thermoplastic resin sheet is too thick, the shapingproperties of the decorating sheet 11 tend to be reduced. When thethermoplastic resin sheet is too thin, it tends to be difficult todetach the thermoplastic resin sheet 12 from the decorating sheet 11after preform molding.

As shown in FIG. 3A, the superposed body 13 is softened by being heatedwith heaters H. The heating temperature with the heaters H is atemperature that allows the shape of the superposed body 13 to bechanged so as to follow the shape of a mold M1 of a vacuum moldingmachine M shown in FIG. 3B, without causing complete melting, and can beselected from the range of 100 to 180° C., for example.

The heated and softened superposed body 13 is subjected to vacuummolding. Specifically, the heated and softened superposed body 13 isdisposed so as to cover the mold M1 of the vacuum molding machine Mshown in FIG. 3B. Then, as shown in FIG. 3C, the softened superposedbody 13 is brought into close contact with the mold M1 of the vacuummolding machine M, and the air between the superposed body 13 and themold M1 is discharged by a vacuum pump P from vacuum holes v formed inthe mold M1, thereby causing the superposed body 13 to be adsorbed bythe mold M1 so as to be tightly attached thereto with atmosphericpressure. Then, the shaped superposed body 13 is cooled and solidified.

Then, as shown in FIG. 3D, a preform molded body 14 is released from themold M1. As shown in FIG. 3E, unnecessary portions N of the preformmolded body 14 are trimmed as needed.

Then, as shown in FIG. 3F, the thermoplastic resin sheet 12 is detached,to give a preform molded body 15.

The preform molded body 15 thus obtained is integrated with a moldedbody to be decorated, to form a decorative molded body. Examples of themethod for integrating the preform molded body with a molded body to bedecorated include in-molding in which the preform molded body isintegrated with a molded body to be decorated, which is a resin moldedbody molded by injection molding, and a method in which a molded body tobe decorated that is molded in advance is bonded to one surface of thepreform molded body via an adhesive.

A method for producing a decorative molded body by in-molding will bedescribed with reference to FIGS. 4A to 4D. Although a method forperforming in-molding using a preform molded body 15 from which thethermoplastic resin sheet 12 has been detached will be described in thepresent embodiment, a preform molded body 15 with the thermoplasticresin sheet 12 attached thereto may be subjected to in-molding, and,thereafter, the thermoplastic resin sheet 12 may be detached.

As shown in FIG. 4A, a mold 17 includes a movable mold 17 a having acavity C, and a fixed mold 17 b. In addition, a stripper plate 17 c isdisposed between the movable mold 17 a and the fixed mold 17 b. First,the preform molded body 15 is disposed in the cavity C.

Although the method for disposing the preform molded body 15 in thecavity C is not particularly limited, it is preferable that the preformmolded body 15 is fixed to the cavity C for the purpose of positioning.When the preform molded body 15 is not fixed to the cavity C, there isthe possibility that the preform molded body 15 may be positionallydisplaced in the cavity C with the flowing of the injected resin duringinjection molding in the subsequent step. Specific examples of themethod for fixing the preform molded body 15 to the cavity C include amethod in which the preform molded body 15 is fixed to the surface ofthe movable mold with a pressure-sensitive adhesive, and a method inwhich the preform molded body 15 is fixed by fitting a hole portion or arecess included in the shape of the preform molded body 4 to a core ofthe movable mold that matches the shape of the hole portion or therecess.

Then, as shown in FIG. 4B, molten resin 16 a is injected into the cavityC by injection molding, thereby molding an in-molded body, which is adecorative molded body in which the preform molded body 15 is integratedon the surface thereof. More specifically, the movable mold 17 a and thefixed mold 17 b are closed, then a cylinder 18 a of an injection moldingmachine 18 is advanced until a nozzle 18 c comes into contact with asprue bushing 17 f of the fixed mold 17 b, and the molten resin 16 amolten in the cylinder 18 a of the injection molding machine is injectedwith a screw 18 b, thereby injecting the molten resin 16 a into thecavity C of the mold 17. The injected molten resin 16 a flows into thecavity C through a resin flow path R inside the mold 17, and is chargedinto the cavity C. At this time, the molten resin 16 a appropriatelypermeates the preform molded body 15, so that the injection-molded body,which is the molded body 16 to be decorated molded by injection molding,is integrated with the preform molded body 15 so as to maintain highadhesion due to an anchoring effect.

As the resin for forming the injection-molded body molded by in-moldinginclude various thermoplastic resins, including, for example, an ABSresin, a polycarbonate resin, polyolefin resins such as polypropylene,polyester resins such as polyethylene terephthalate (PET) andpolybutylene terephthalate, and various polyamide resins can be usedwithout any particular limitation, and these resins are appropriatelyselected according to the application. For example, resins havingexcellent impact resistance, such as an ABS resin, a polycarbonateresin, and a polyolefin resin such as polypropylene are suitably used asthe resin for use in the casings of a mobile phone, a mobile device, ahome electrical appliance and the like.

As the conditions for the injection molding, conditions (resintemperature, mold temperature, injection pressure, injection speed,holding pressure after injection, cooling time) that allow the resin toflow to the flow terminal end may be selected as appropriate accordingto the melting point and the melt viscosity of the injected resin, theshape of the molded body, and the resin thickness.

Then, after completion of the injection, the molten resin 16 a iscooled, to form an injection-molded body, which is the molded body 16 tobe decorated, as shown in FIG. 4C. Thus, a decorative molded body 30 inwhich the preform molded body 15 is integrated with the molded body 16to be decorated is molded. Then, by opening the mold 17, the movablemold 17 a and the fixed mold 17 b are separated from each other. Then, adecorative molded body 30 as shown in FIG. 4D is taken out. Thus, thedecorative molded body 30 in which the molded body 16 to be decorated,which is an injection-molded body, is integrated with one surface of thepreform molded body 15 is obtained.

In the decorative molded body thus obtained, a napped artificial leatherincluding an artificial leather base material dyed with a cationic dyeis stacked and integrated on the surface layer. In such a decorativemolded body, the contamination by the cationic dye due to heating duringproduction or use is suppressed even when a light-color or white, ortransparent molded body to be decorated such as the one with a lightnessL* value of >50, or even a lightness L* value of >70 is used. In thedecorative molded body, ΔL*, which is a difference in L* value betweenthe decorating sheet and the molded body to be decorated, is preferably10 or more, more preferably 20 or more, particularly preferably 30 ormore, because of the excellent design quality due to a color with anexcellent contrast. Such a decorative molded body can be suitably usedas the casings of a mobile phone, a smartphone, various mobile devices,a home electrical appliance and the like, the interior members of avehicle, an aircraft and the like, and the exterior members of abuilding material, an article of furniture and the like.

Furthermore, FIG. 5 is a schematic cross-sectional view of a decorativemolded body 50 including a resin layer-equipped artificial leather 40that uses an artificial leather base material 41 including a surfacewith a lightness L* value of ≤50, and a fiber base material includingcationic dye-dyeable polyester fibers and an elastic polymer, the resinlayer-equipped artificial leather 40 being dyed with a cationic dye. InFIG. 5, the artificial leather base material 41 dyed with a cationic dyethat has a lightness L* value of ≤50 is finished into a resinlayer-equipped artificial leather 40 by stacking and integrating a resinlayer 42 on the surface thereof. Then, the artificial leather basematerial 41 is bonded to a resin molded body 43 via an adhesive layer44. The decorative molded body 50 has an opening H. A cross section E1of the opening H and an end face E2 of the decorative molded body 50 areexposed to the outside, and constitute portions that can be visuallyrecognized by the user.

Since the wall surface of the opening H of the decorative molded body 50and the end face E2 of the decorative molded body 50 constitute portionsthat can be visually recognized by the user, the fiber base materialincluded in the artificial leather base material 41 may be required tobe colored, from the viewpoint of design quality. When the artificialleather base material 41 as described above is used to produce such adecorative molded body 50, the cationic dye is less likely to migratefrom the dark-color artificial leather base material 41 to the resinlayer 42 and the resin molded body 43.

EXAMPLES

Hereinafter, the present invention will be described more specificallyby way of examples. It should be appreciated that the scope of thepresent invention is by no means limited by the examples.

Examples of Napped Artificial Leather and Resin Layer-EquippedArtificial Leather Example 1

A non-woven fabric obtained by three-dimensionally entanglingcontinuous, island-in-the-sea composite fibers was produced, with thenon-woven fabric including ethylene-modified polyvinyl alcohol (PVA;ethylene unit content: 8.5 mol %, polymerization degree: 380,saponification degree: 98.7 mol %) as a thermoplastic resin serving as asea component, and polyethylene terephthalate (PET) modified with atetrabutylphosphonium salt of sulfoisophthalic acid (containing 1.7 mol% of a tetrabutylphosphonium salt unit of sulfoisophthalic acid, 5 mol %of a 1,4-cyclohexane dicarboxylic acid unit, 5 mol % of an adipic acidunit; glass transition temperature: 62° C.) as a thermoplastic resinserving as an island component, and the mass ratio between the seacomponent and the island component being sea component/islandcomponent=25/75.

Then, the non-woven fabric obtained by three-dimensionally entanglingthe island-in-the-sea composite fibers was impregnated with apolyurethane emulsion (emulsion composed mainly of polycarbonate/etherpolyurethane with a polyurethane solid concentration of 30%), and wasdried in a drying furnace at 150° C., thereby applying polyurethane tothe non-woven fabric. Then, the sea component included in theisland-in-the-sea composite fibers was removed by extraction byimmersing the non-woven fabric in which the island-in-the-sea compositefibers to which polyurethane had been applied were three-dimensionallyentangled in hot water at 95° C. for 20 minutes, and the non-wovenfabric was dried in a drying furnace at 120° C., thereby obtaining afiber base material including the non-woven fabric of the cationicdye-dyeable polyester fibers with a fineness of 0.2 dtex that had beenimpregnated with polyurethane. The obtained fiber base material had amass ratio of non-woven fabric/polyurethane of 90/10. Then, the fiberbase material was sliced into halves, and the surface thereof was nappedby being buffed with sand paper with a grit number of 600. The nappedfiber base material had a fineness of 0.2 dtex, a polyurethane ratio of10 mass %, a thickness of 0.78 mm, and an apparent density 0.51 g/cm³.

Then, the napped fiber base material was dyed into red by being immersedin a dyeing bath storing a 90° C. dye liquid containing 19% owf ofNichilon Red-GL (manufactured by NISSEI KASEI CO., LTD.) as a cationicdye and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratioof 1:30 for 40 minutes. Then, the step of soaping the napped fiber basematerial in the same dyeing bath at 70° C. using a hot water bathcontaining 2 g/L of Sordine R as an anionic surfactant was repeatedtwice. Then, after the soaping, the napped fiber base material wasdried, thereby obtaining a dyed suede-like artificial leather.

Thus, a dark-red suede-like artificial leather (suede-like artificialleather base material) including a non-woven fabric of cationicdye-dyeable polyester fibers with a fineness of 0.2 dtex was obtained.The obtained suede-like artificial leather had a thickness of 0.83 mmand an apparent density of 0.47 g/cm³. Then, various properties of thesuede-like artificial leather were evaluated as follows.

(Cationic Dye Content of Suede-Like Artificial Leather)

The cationic dye content of the suede-like artificial leather wasquantitatively determined by the following method.

Before dyeing the napped fiber base material, the prepared dye liquidwas collected, and five diluted dye liquids at different concentrationswith dilution ratios of 10 to 100 were prepared. Then, the absorbancefor the region with a wavelength of 380 to 780 nm of each of the fivediluted dye liquids was measured with a spectrophotometer (U-3010manufactured by Hitachi High-Tech Science Corporation) for every 1 nm,and the measured values were added up, thereby creating a calibrationcurve of the absorbance with respect to the dye concentration (g/L). Thedye liquid (residual dye liquid) in the dyeing bath after dyeing wascollected, and the absorbance for the region with a wavelength of 380 to780 nm was measured for every 1 nm, and the measured values were addedup, thereby determining the dye concentration C (g/L) of the residualdye liquid from the calibration curve. The dye concentration C1 (g/L) inthe cleaning solution after the first soaping and the dye concentrationC2 (g/L) in the cleaning solution after the second soaping weredetermined in the same manner.

The mass of the dyed napped fiber base material is represented as S (g),the amount of the dye dissolved in the dye liquid to achieve the targetowf % is represented as P (g), and the amount of the liquid used whenthe bath ratio to the napped fiber base material was adjusted isrepresented as W(L). Also, the amount of the liquid used for the firstsoaping is represented as W1 (L), and the dye removal amount P1 (g) bythe first soaping was calculated from the equation: P1=W1×C1. The dyeremoval amount P2 (g) by the second soaping was also calculated in thesame manner.

Then, the attached amount of the cationic dye was calculated as thecationic dye content per 100 parts by mass of the napped fiber basematerial from the equation: attached amount X (g)=100×(P−C×W−(P1+P2))/S.

(L* Value)

Using a spectrophotometer (CM-3700 manufactured by Minolta), thelightness L* was determined in accordance with JIS Z 8729 from thecoordinate values of the L*a*b* color system on the surface of a cut-outpiece of the suede-like artificial leather. The value was an average ofthe values for three points evenly selected from average positions ofthe test piece.

(Thickness)

The thickness of the suede-like artificial leather was measured inaccordance with a JIS method. Using a thickness measurement instrument,the thicknesses of five different portions of the sample were measuredunder the pressurization condition of a load of 23.5 KPa for 10 seconds,and an average value of the measured thicknesses was calculated, afterwhich the value was rounded at the third decimal place.

(Softness)

The bending resistance of the suede-like artificial leather was measuredusing a softness tester (leather softness measuring instrument ST 300:manufactured by the United Kingdom, MSA Engineering Systems Limited).Specifically, a predetermined ring with a diameter of 25 mm was set on alower holder of the device, and thereafter, the suede-like artificialleather was set on the lower holder. Then, a metal pin (diameter: 5 mm)fixed to an upper lever was pressed down toward the suede-likeartificial leather. Then, the upper lever was pressed down, and thevalue at the time when the upper lever was locked was read. Note thatthe value indicated the penetration depth, and the larger the value, thesuppler the leather was.

(Color Migration to Polyvinyl Chloride (PVC) Film by PressurizationUnder Heating)

A polyvinyl chloride film (white, ΔL*=85.0) with a thickness of 0.8 mmwas placed on top of the surface of a cut-out piece of the suede-likeartificial leather, and was uniformly pressurized such that a load of750 g/cm² was applied. Then, the film was left for 16 hours at 50° C.under an atmosphere of a relative humidity of 15%. Then, the colordifference ΔE* between the polyvinyl chloride film before colormigration and the polyvinyl chloride film after color migration wasmeasured using a spectrophotometer, and the measured value was evaluatedaccording to the following criteria:

Grade 5: 0.0≤ΔE*≤0.2

Grade 4-5: 0.2<ΔE*≤1.4

Grade 4: 1.4<ΔE*≤2.0

Grade 3-4: 2.0<ΔE*≤3.0

Grade 3: 3.0<ΔE*≤3.8

Grade 2-3: 3.8<ΔE*≤5.8

Grade 2: 5.8<ΔE*≤7.8

Grade 1-2: 7.8<ΔE*≤11.4

Grade 1: 11.4<ΔE*

(Color Migration Test Using Solvent (Methyl Ethyl Ketone (MEK)))

The suede-like artificial leather is cut out into a piece of 2.45 cmlong by 2.45 cm wide, and the cut-out piece was sandwiched between thesurfaces of measurement white cloths, and the cut-out piece and themeasurement white cloth were stapled together at four locations on theupper, lower, left and right sides, to produce a test base material.Then, the test base material is immersed in MEK placed in a glasscontainer for 20 seconds, and thereafter taken out, and air-dried. Afterthe drying, the state of contamination to the measurement white clothwas evaluated. As for the evaluation, the most contaminated portion,regardless of whether it was located on the front or the back, wasvisually evaluated according to the JIS gray-scale standard, and ratedusing degrees 1 to 5.

(Color Migration of Resin Layer-Equipped Artificial Leather)

A polyurethane film (white, ΔL*=92.9) with a thickness of 250 μm waspressure-bonded to the surface of the suede-like artificial leather viaa polyurethane adhesive under 5 Kg/cm² at 130° C. for 1 minute, to forma resin layer-equipped artificial leather. Then, the resinlayer-equipped artificial leather was heat-treated under 20 Kg/cm² at150° C. for 1 minute. The color difference ΔE* of the urethane filmbefore and after the heat treatment of the resin layer-equippedartificial leather was measured using a spectrophotometer, and evaluatedaccording to the following criteria:

Grade 5: 0.0≤ΔE*≤0.2

Grade 4-5: 0.2<ΔE*≤1.4

Grade 4: 1.4<ΔE*≤2.0

Grade 3-4: 2.0<ΔE*≤3.0

Grade 3: 3.0<ΔE*≤3.8

Grade 2-3: 3.8<ΔE*≤5.8

Grade 2: 5.8<ΔE*≤7.8

Grade 1-2: 7.8<ΔE*≤11.4

Grade 1: 11.4<ΔE*

(Surface Touch)

The suede-like artificial leather was cut-out into a piece of 30 cm longby 20 cm wide, to prepare a sample. Then, the tactile impression of thesurface when rubbed by the palm of a hand was evaluated according to thefollowing criteria:

A: The surface had no irregularities or roughness, and a smooth and wetfeel was observed.

B: The surface had some irregularities and roughness.

C: The surface had significant irregularities and roughness, and a dryfeel was observed.

(Texture)

The suede-like artificial leather was cut-out into a piece of 30 cm longby 20 cm wide, to prepare a sample. Then, the tactile impression of thesample when grabbed was evaluated according to the following criteria:

A: The sample was rounded, and created almost no sharp-edged creaseswhen grabbed.

B: The sample showed some sharp-edged creases when grabbed.

C: The sample was in the state of being sharp-edged when grabbed, like asheet of paper.

The results are shown in Table 1.

TABLE 1 Dye content Example Fineness Polyurethane Presence of (parts byL* Thickness No. (dtex) ratio (mass %) Dye type owf % soaping mass)value (mm) Softness 1 0.2 10 Cationic dye 19 Yes 18.0 37 0.83 3.0 2 2.05 Cationic dye 6 Yes 5.9 37 1.19 2.8 3 3.3 5 Cationic dye 4.7 Yes 4.7 371.02 2.9 4 4.2 5 Cationic dye 4.1 Yes 4.1 37 1.06 2.8 5 0.08 10 Cationicdye 30 Yes 21.6 45 0.82 3.4 6 0.2 10 Cationic dye 6 Yes 5.9 43 0.83 3.07 5.1 5 Cationic dye 3.8 Yes 3.8 37 1.05 2.7 8 0.2 10 Cationic dye 19 No18.3 37 0.83 3.0 9 0.2 10 Cationic dye 6 No 6.0 43 0.83 3.0 Com. Ex. 10.2 11 Disperse dye 19 Yes 19 35 0.83 3.0 Com. Ex. 2 2.0 5 Disperse dye6 Yes 6 35 1.04 2.8 Com. Ex. 3 0.14 10 Cationic dye 1.0 Yes 1.0 64 0.823.4 Color migration to Color migration of Product of Apparent PVC byheating and resin layer-equipped Example softness and densitypressurization Color migration by Surface artificial leather No.thickness (g/cm³) (grade) solvent (grade) touch Texture (grade) 1 2.490.47 4-5 3 A A 4 2 3.33 0.40 4-5 4 B A 4-5 3 2.96 0.40 5 4-5 B A 4-5 42.97 0.39 5 4-5 B B 4-5 5 2.79 0.48 3-4 1-2 A A 3 6 2.49 0.47 4-5 4 A A4 7 2.84 0.38 5 4-5 C C 4-5 8 2.49 0.47 4 1 A A 4 9 2.49 0.47 4-5 3 A A4 Com. Ex. 1 2.49 0.48 2-3 1 A A 1-2 Com. Ex. 2 2.91 0.40 3-4 1-2 B A2-3 Com. Ex. 3 2.79 0.48 5 4-5 A A 4-5

Example 2

In place of the napped fiber base material produced in Example 1, anapped fiber base material was obtained in the same manner as in Example1, except that the napped fiber base material included a non-wovenfabric of cationic dye-dyeable polyester fibers with a fineness of 2.0dtex, and had a polyurethane ratio of 5 mass %, a thickness of 0.82 mm,and an apparent density of 0.46 g/cm³. Then, the obtained napped fiberbase material was dyed into red by being immersed in a 90° C. dyeingbath containing 6% owf of Nichilon Red-GL (manufactured by NISSEI KASEICO., LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as adyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the stepof soaping the napped fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the napped fiberbase material was dried, thereby obtaining a dyed suede-like artificialleather. Thus, a dyed dark-red suede-like artificial leather including anon-woven fabric of cationic dye-dyeable polyester fibers with afineness of 2.0 dtex was obtained. The obtained suede-like artificialleather had a thickness of 1.19 mm and an apparent density of 0.40g/cm³. Then, various properties of the suede-like artificial leatherwere evaluated in the same manner as in Example 1. The results are shownin Table 1.

Example 3

In place of the napped fiber base material produced in Example 1, anapped fiber base material was obtained in the same manner as in Example1, except that the napped fiber base material included a non-wovenfabric of cationic dye-dyeable polyester fibers with a fineness of 3.3dtex, and had a polyurethane ratio of 5 mass %, a thickness of 0.75 mm,and an apparent density of 0.46 g/cm³. Then, the obtained napped fiberbase material was dyed into red by being immersed in a 90° C. dyeingbath containing 4.7% owf of Nichilon Red-GL (manufactured by NISSEIKASEI CO., LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acidas a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, thestep of soaping the napped fiber base material in the same dyeing bathat 70° C. using a hot water bath containing 2 g/L of Sordine R as ananionic surfactant was repeated twice. Then, after the soaping, thenapped fiber base material was dried, thereby obtaining a dyedsuede-like artificial leather. Thus, a dyed dark-red suede-likeartificial leather including a non-woven fabric of cationic dye-dyeablepolyester fibers with a fineness of 3.3 dtex was obtained. The obtainedsuede-like artificial leather had a thickness of 1.02 mm and an apparentdensity of 0.40 g/cm³. Then, various properties of the suede-likeartificial leather were evaluated in the same manner as in Example 1.The results are shown in Table 1.

Example 4

In place of the napped fiber base material produced in Example 1, anapped fiber base material including a non-woven fabric of cationicdye-dyeable polyester fibers with a fineness of 4.2 dtex, and having apolyurethane ratio of 5 mass %, a thickness of 0.75 mm, and an apparentdensity 0.45 g/cm³ was produced. Then, the obtained napped fiber basematerial was dyed into red by being immersed in a 90° C. dyeing bathcontaining 4.1% owf of Nichilon Red-GL (manufactured by NISSEI KASEICO., LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as adyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the stepof soaping the napped fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the napped fiberbase material was dried, thereby obtaining a dyed suede-like artificialleather. Thus, a dyed dark-red suede-like artificial leather including anon-woven fabric of cationic dye-dyeable polyester fibers with afineness of 4.2 dtex was obtained. The obtained suede-like artificialleather had a thickness of 1.06 mm and an apparent density of 0.39g/cm³. Then, various properties of the suede-like artificial leatherwere evaluated in the same manner as in Example 1. The results are shownin Table 1.

Example 5

In place of the napped fiber base material produced in Example 1, anapped fiber base material including a non-woven fabric of cationicdye-dyeable polyester fibers with a fineness of 0.08 dtex, and having apolyurethane ratio of 10 mass %, a thickness of 0.75 mm, and an apparentdensity 0.52 g/cm³ was produced. Then, the obtained napped fiber basematerial was dyed into red by being immersed in a 90° C. dyeing bathcontaining 30% owf of Nichilon Red-GL (manufactured by NISSEI KASEI CO.,LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as adyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the stepof soaping the napped fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the napped fiberbase material was dried, thereby obtaining a dyed dark-red suede-likeartificial leather. Thus, a dyed suede-like artificial leather includinga non-woven fabric of cationic dye-dyeable polyester fibers with afineness of 0.08 dtex was obtained. The obtained suede-like artificialleather had a thickness of 0.82 mm and an apparent density of 0.48g/cm³. Then, various properties of the suede-like artificial leatherwere evaluated in the same manner as in Example 1. The results are shownin Table 1.

Example 6

A napped fiber base material obtained in the same manner as in Example 1was dyed in the same manner as in Example 1 except that dyeconcentration was changed from 19% owf to 6% owf, to obtain a dyeddark-red suede-like artificial leather. Then, various properties of thesuede-like artificial leather were evaluated in the same manner as inExample 1. The results are shown in Table 1.

Example 7

In place of the napped fiber base material produced in Example 1, anapped fiber base material including a non-woven fabric of cationicdye-dyeable polyester fibers with a fineness of 5.1 dtex, and having apolyurethane ratio of 5 mass %, a thickness of 0.78 mm, and an apparentdensity 0.44 g/cm³ was produced. Then, the obtained napped fiber basematerial was dyed into red by being immersed in a 90° C. dyeing bathcontaining 3.8% owf of Nichilon Red-GL (manufactured by NISSEI KASEICO., LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as adyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the stepof soaping the napped fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the napped fiberbase material was dried, thereby obtaining a dyed suede-like artificialleather. Thus, a dyed dark-red suede-like artificial leather including anon-woven fabric of cationic dye-dyeable polyester fibers with afineness of 5.1 dtex was obtained. The obtained suede-like artificialleather had a thickness of 1.05 mm and an apparent density of 0.38g/cm³. Then, the suede-like artificial leather were evaluated in thesame manner as in Example 1. The results are shown in Table 1.

Example 8

A dyed dark-red suede-like artificial leather including a non-wovenfabric of cationic dye-dyeable polyester fibers was obtained in the samemanner as in Example 1, except that the napped fiber base material waswashed with water at 70° C., instead of repeating twice the step ofsoaping the napped fiber base material at 70° C. using a hot water bathcontaining 2 g/L of Sordine R as an anionic surfactant in Example 1.Then, the suede-like artificial leather was evaluated in the same manneras in Example 1. The results are shown in Table 1.

Example 9

A dyed dark-red suede-like artificial leather including a non-wovenfabric of cationic dye-dyeable polyester fibers was obtained in the samemanner as in Example 6, except that the napped fiber base material waswashed with water at 70° C., instead of repeating twice the step ofsoaping the napped fiber base material at 70° C. using a hot water bathcontaining 2 g/L of Sordine R as an anionic surfactant in Example 6.Then, the suede-like artificial leather was evaluated in the same manneras in Example 1. The results are shown in Table 1.

Comparative Example 1

A napped fiber base material including a non-woven fabric of polyesterfibers with a fineness of 0.2 dtex for which isophthalic acid-modifiedPET (containing 6 mol % of an isophthalic acid unit) was used as athermoplastic resin serving as an island component, and having apolyurethane ratio of 11 mass %, a thickness of 0.78 mm, and an apparentdensity of 0.51 g/cm³ was produced. Then, the fiber base material wasjet-dyed with D. Red-W, Kiwalon Rubin 2GW, and Kiwalon Yellow 6GFserving as disperse dyes at 130° C. for 1 hour, and reductively cleanedin the same dyeing bath, to obtain a dyed dark-red suede-like artificialleather. Then, the suede-like artificial leather was evaluated in thesame manner as in Example 1. The results are shown in Table 1.

Comparative Example 2

A fiber base material including a non-woven fabric of polyester fiberswith a fineness of 2 dtex for which isophthalic acid-modified PET(containing 6 mol % of an isophthalic acid unit) was used as thethermoplastic resin serving as the island component, and having apolyurethane ratio of 5 mass %, a thickness of 0.78 mm, and an apparentdensity of 0.40 g/cm³ was produced. Then, the fiber base material wasjet-dyed with D. Red-W, Kiwalon Rubin 2GW, and Kiwalon Yellow 6GFserving as disperse dyes at 130° C. for 1 hour, and reductively cleanedin the same dyeing bath, to obtain a dyed dark-red suede-like artificialleather. Then, the suede-like artificial leather was evaluated in thesame manner as in Example 1. The results are shown in Table 1.

Comparative Example 3

In place of the fiber base material produced in Example 1, a nappedfiber base material including a non-woven fabric of cationic dye-dyeablepolyester fibers with a fineness of 0.14 dtex, and having a polyurethaneratio of 10 mass %, a thickness of 0.78 mm, and an apparent density 0.51g/cm³ was produced. Then, the obtained fiber base material was dyed intored by being immersed in a 90° C. dyeing bath containing 3.8% owf ofNichilon Red-GL (manufactured by NISSEI KASEI CO., LTD.) serving as acationic dye, and 1 g/L of 90% acetic acid as a dyeing assistant at abath ratio of 1:30 for 40 minutes. Then, the step of soaping the nappedfiber base material in the same dyeing bath at 70° C. using a hot waterbath containing 2 g/L of Sordine R as an anionic surfactant was repeatedtwice. Then, after the soaping, the fiber base material was dried,thereby obtaining a dyed light-red suede-like artificial leatherincluding a non-woven fabric of cationic dye-dyeable polyester fiberswith a fineness of 0.14 dtex. The obtained suede-like artificial leatherhad a thickness of 0.82 mm and an apparent density of 0.48 g/cm³. Then,the suede-like artificial leather were evaluated in the same manner asin Example 1. The results are shown in Table 1.

Examples of Decorating Sheet and Decorative Molded Body Example 10

A non-woven fabric obtained by three-dimensionally entanglingcontinuous, island-in-the-sea composite fibers was produced, with thenon-woven fabric including ethylene-modified polyvinyl alcohol (PVA;ethylene unit content: 8.5 mol %, polymerization degree: 380,saponification degree: 98.7 mol %) as a thermoplastic resin serving as asea component, and polyethylene terephthalate (PET) modified with atetrabutylphosphonium salt of sulfoisophthalic acid (containing 1.7 mol% of a tetrabutylphosphonium salt unit of sulfoisophthalic acid, 5 mol %of a 1,4-cyclohexane dicarboxylic acid unit, 5 mol % of an adipic acidunit; glass transition temperature: 62° C.) as a thermoplastic resinserving as an island component, and the mass ratio between the seacomponent and the island component being sea component/islandcomponent=25/75.

Then, the non-woven fabric obtained by three-dimensionally entanglingthe island-in-the-sea composite fibers was impregnated with apolyurethane emulsion (emulsion composed mainly of polycarbonate/etherpolyurethane with a polyurethane solid concentration of 30%), and wasdried in a drying furnace at 150° C., thereby applying polyurethane tothe non-woven fabric. Then, the sea component was removed by extractionby immersing the non-woven fabric of the island-in-the-sea compositefibers to which polyurethane had been applied in hot water at 95° C. for20 minutes, and the non-woven fabric was dried in a drying furnace at120° C., thereby obtaining a non-woven fabric of the cationicdye-dyeable polyester fibers that had been impregnated withpolyurethane. The non-woven fabric to which polyurethane had beenapplied was sliced into halves, then the surface thereof was buffed withsand paper with a grit number of 600, and the non-woven fabric wasthereby finished into a suede-like fiber base material. The fiber basematerial had a fineness of 0.08 dtex, a polyurethane content ratio of 10mass %, a thickness of 0.5 mm, and an apparent density 0.55 g/cm³.

Then, the fiber base material was dyed into red by being immersed in a90° C. dye liquid containing 18% owf of Nichilon Red-GL (manufactured byNISSEI KASEI CO., LTD.) as a cationic dye and 1 g/L of 90% acetic acidas a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, thestep of soaping the fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the fiber basematerial was dried, thereby obtaining a dark-red suede-like artificialleather dyed with a cationic dye.

Thus, a decorating sheet, which was a dyed dark-red suede-likeartificial leather dyed with a cationic dye that included a fiber basematerial including a non-woven fabric of cationic dye-dyeable polyesterfibers with 0.08 dtex and polyurethane was obtained. The suede-likeartificial leather had a thickness of 0.55 mm and an apparent density of0.50 g/cm³. The L* value was 36. Then, various properties of thesuede-like artificial leather were evaluated as follows.

(L* Value)

Using a spectrophotometer (CM-3700 manufactured by Minolta), thelightness L* was determined in accordance with JIS Z 8729 from thecoordinate values of the L*a*b* color system on the surface of a cut-outpiece of the suede-like artificial leather. The value was an average ofthe values for three points evenly selected from average positions ofthe test piece.

(Water Fastness)

A water fastness test for a cotton cloth in accordance with a JIS method(JIS L 0846) was performed. Specifically, a test piece of 6 cm by 6 cmwas cut out from the suede-like artificial leather. Then, the test piecewas immersed in water at room temperature, and thereafter attached to asweat testing machine. The test piece was held in a dryer machine at37±2° C. for 4 hours under a load of about 45 N. Then, the fastness ofthe test piece was evaluated by making comparison with the contaminationgray scale. Then, the grade at that time was determined.

Then, the obtained decorating sheet was molded using a mold having acavity for obtaining a preform molded body. Specifically, the preformmolded body was a saucer-shaped molded body having a height of 7 mm fromthe bottom surface to the outer surface, which simulated a smartphonecover, as shown in FIG. 6.

Specifically, a transparent acrylic sheet with a thickness of 75 μm wasplaced on one surface of the decorating sheet, to form a superposedbody. Then, the superposed body was heated to a temperature of 150° C.with an infrared heater, and was subjected to vacuum pressure molding ata predetermined air pressure using molds having various shapes. Throughvacuum pressure molding, a preform molded body with a thermoplasticresin sheet in which the surface of the transparent acrylic sheet andthe decorating sheet forming the superposed body were thermallycompressed was obtained. Then, the transparent acrylic sheet wasdetached from the preform molded body with a thermoplastic resin sheet,to obtain a preform molded body.

Then, in-molding was performed using the obtained preform molded body.Specifically, an in-molding mold having a shape corresponding to theshape of the preform molded body was prepared. Then, the mold wasmounted on an injection molding machine, and the preform molded body wasdisposed in a cavity of the mold. Then, a milk-white ABS resin (TOYOLACABS700 manufactured by Toray Industries Inc.) was injection-molded at aresin temperature of 240° C. and a mold temperature of 50° C. Adecorative molded body was obtained by performing in-mold in thismanner. Note that the L* value of the injection-molded body to bedecorated was 92.

Another decorative molded body was also produced in the same mannerexcept that a clear-color polycarbonate (Iupilon 52000 manufactured byMitsubishi Engineering-Plastics Corporation) was used in place of theABS resin, and that the conditions were changed such that the resintemperature was 280° C. and the mold temperature was 80° C. The L* valueof the injection-molded decorated molded body was 93.

Then, the color migration of the decorative molded body was evaluatedaccording to the following evaluation method.

(Evaluation of Dye Migration by Molding of Decorative Molded Body)

The decorative molded body thus molded was observed visually, and thedye migration of the decorated molded body was evaluated using thecontamination gray scale, and rated using grades 1 (significantcontamination) to 5 (no contamination).

(Evaluation of Color Migration of Decorative Molded Body by AcceleratedTesting)

A decorating sheet was placed on top of the surface of an ABS resin orpolycarbonate rectangular plate of 30 mm×50 mm having a thickness of 1.5mm, and was uniformly pressurized so as to apply a load of 7.5 g/cm²thereto. Then, the whole was left under an atmosphere of 70° C. and 95%RH for 24 hours. Then, the color difference ΔE* between the rectangularplate before being left and the rectangular plate after being left wasmeasured with a spectrophotometer, and was evaluated according to thefollowing criteria.

Grade 5: 0.0≤ΔE*≤0.2

Grade 4-5: 0.2<ΔE*≤1.4

Grade 4: 1.4<ΔE*≤2.0

Grade 3-4: 2.0<ΔE*≤3.0

Grade 3: 3.0<ΔE*≤3.8

Grade 2-3: 3.8<ΔE*≤5.8

Grade 2: 5.8<ΔE*≤7.8

Grade 1-2: 7.8<ΔE*≤11.4

Grade 1: 11.4<ΔE*

The results are shown in Table 2 below.

TABLE 2 Example No. Ex. 10 Ex. 11 Ex. 12 Ex. 13 Com. Ex. 4 Com. Ex. 5Fineness 0.08 0.08 0.2 0.08 0.08 0.08 (dtex) Polyurethane 10 10 10 10 1010 ratio (mass %) owf % 18 5 6 18 12 13 Decorating sheet Water fastness(grade) 4-5 4 4-5 4 4-5 4-5 L* value 36 47 42 33 34 30 Color migration 55 5 3-4 1 1 to ABS during molding Color migration 5 5 5 4 1 1 to PCduring molding Accelerated 5 5 5 3 2 2 testing of color migration to ABSduring molding (ΔE) Accelerated 4-5 5 5 3-4 2 2 testing of colormigration to PC during molding (ΔE)

Example 11

A decorating sheet was obtained by dyeing the suede-like fiber basematerial in the same manner as in Example 10 except that dyeing wasperformed in Example 10 under the following dyeing conditions.

The fiber base material was dyed into blue by being immersed in a 90° C.dye liquid containing 5% owf of Nichilon Blue-AZN (manufactured byNISSEI KASEI CO., LTD.) as a cationic dye and 1 g/L of 90% acetic acidas a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, thestep of soaping the fiber base material in the same dyeing bath at 70°C. using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the fiber basematerial was dried, thereby obtaining a dyed suede-like artificialleather.

Thus, a decorating sheet, which was a dyed dark-blue suede-likeartificial leather dyed with a cationic dye that included a fiber basematerial including a non-woven fabric of cationic dye-dyeable polyesterfibers with 0.08 dtex and polyurethane was obtained. The suede-likeartificial leather had a thickness of 0.83 mm and an apparent density of0.47 g/cm³. The L* value was 47.

Then, a preform molded body and a decorative molded body were molded inthe same manner as in Example 10, except that the obtained decoratingsheet was used in place of the decorating sheet obtained in Example 10,and the preform molded body and the decorative molded body wereevaluated in the same manner as in Example 10. The results are shown inTable 2.

Example 12

In place of the suede-like fiber base material produced in Example 10, asuede-like fiber base material including a non-woven fabric of cationicdye-dyeable polyester fibers with a fineness of 0.2 dtex, and having apolyurethane ratio of 10 mass %, a thickness of 0.82 mm, and an apparentdensity of 0.46 g/cm³ was produced. Then, the obtained fiber basematerial was dyed into red by being immersed in a 90° C. dye liquidcontaining 6% owf of Nichilon Red-GL (manufactured by NISSEI KASEI CO.,LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as adyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the stepof soaping the fiber base material in the same dyeing bath at 70° C.using a hot water bath containing 2 g/L of Sordine R as an anionicsurfactant was repeated twice. Then, after the soaping, the fiber basematerial was dried, to obtain a decorating sheet, which was a suede-likeartificial leather. Thus, a decorating sheet, which was a dark-redsuede-like artificial leather dyed with a cationic dye that included afiber base material including a non-woven fabric of cationic dye-dyeablepolyester fibers with a fineness of 0.2 dtex and polyurethane wasobtained. The suede-like artificial leather had a thickness of 1.19 mmand an apparent density of 0.40 g/cm³. In addition, the L* value was 42.

Then, a preform molded body and a decorative molded body were molded inthe same manner as in Example 10, except that the obtained decoratingsheet was used in place of the decorating sheet obtained in Example 10,and were evaluated in the same manner as in Example 10. The results areshown in Table 2.

Example 13

A decorating sheet, which was a suede-like artificial leather, wasobtained by dyeing the suede-like fiber base material in the same manneras in Example 10, except that dyeing was performed under the followingdyeing conditions in Example 10.

The suede-like fiber base material was dyed into blue by being immersedin a 90° C. dye liquid containing 5% owf of Nichilon Blue-AZN(manufactured by NISSEI KASEI CO., LTD.) as a cationic dye, and 1 g/L of90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40minutes. Then, washing with water was performed once in the same dyeingbath at 70° C. Then, the suede-like fiber base material was dried, toobtain a decorating sheet, which was a dark-blue suede-like artificialleather dyed with a cationic dye.

The suede-like artificial leather had a thickness of 0.83 mm and anapparent density of 0.47 g/cm³. In addition, the L* value was 33. Then,a preform molded body and a decorative molded body were molded in thesame manner as in Example 10, except that the obtained decorating sheetwas used in place of the decorating sheet obtained in Example 10, andwere evaluated in the same manner as in Example 10. The results areshown in Table 2.

Comparative Example 4

A suede-like fiber base material including a non-woven fabric to whichpolyurethane had been applied was obtained in the same manner as inExample 10, except that isophthalic acid-modified PET (containing 6 mol% of an isophthalic acid unit) was used as the thermoplastic resinserving as the island component. Then, the suede-like fiber basematerial was jet-dyed with D. Red-W, Kiwalon Rubin 2GW, and KiwalonYellow 6GF serving as disperse dyes at 130° C. for 1 hour, andreductively cleaned in the same dyeing bath, to obtain a decoratingsheet, which was a dyed dark-red suede-like artificial leather. Then,the obtained decorating sheet was evaluated in the same manner as inExample 10. The results are shown in Table 2.

Comparative Example 5

A suede-like fiber base material including a non-woven fabric to whichpolyurethane had been applied was obtained in the same manner as inExample 10, except that isophthalic acid-modified PET (containing 6 mol% of an isophthalic acid unit) was used as the thermoplastic resinserving as the island component. Then, the suede-like fiber basematerial was jet-dyed with D Blue HLA, D Red HLA, and D Yellow HLAserving as disperse dyes at 130° C. for 1 hour, and reductively cleanedin the same dyeing bath, to obtain a decorating sheet, which was a dyeddark-blue suede-like artificial leather. Then, the obtained decoratingsheet was evaluated in the same manner as in Example 10. The results areshown in Table 2.

REFERENCE SIGNS LIST

-   1 . . . Artificial leather base material-   2 . . . Resin layer-   3 . . . Rubber sole (resin layer)-   3 a, 5 a . . . Adhesive layer-   5 . . . Patch (resin layer)-   7, 8, 10 . . . Resin layer-equipped artificial leather-   11 . . . Decorating sheet-   12 . . . Thermoplastic resin sheet-   13 . . . Superposed body-   14, 15 . . . Preform molded body-   16 . . . Molded body to be decorated-   20 . . . Shoe-   30 . . . Decorative molded body

INDUSTRIAL APPLICABILITY

With the artificial leather base material according to the presentinvention, the surface of a resin molded body, including, for example, aportable terminal body (smartphone, tablet PC) and accessories thereofsuch as a case and a cover, the casing of an electronic device, avehicle interior material, and a cosmetics case, can be decorated like adark-color artificial leather. Furthermore, the artificial leather basematerial according to the present invention can be suitably used forskin members of clothing, shoes, articles of furniture, car seats,general merchandise and the like as a resin layer-equipped artificialleather and a napped artificial leather.

1. An artificial leather base material comprising: a fiber base materialthat comprises cationic dye-dyeable polyester fibers and an elasticpolymer, wherein the artificial leather base material is dyed with atleast one cationic dye and has a surface with a lightness L* value of≤50.
 2. The artificial leather base material according to claim 1,wherein the fiber base material comprises a non-woven fabric of thecationic dye-dyeable polyester fibers and the elastic polymer.
 3. Theartificial leather base material according to claim 1, wherein theartificial leather base material has a grade of color difference,determined in an evaluation of color migration to a white polyvinylchloride film with a thickness of 0.8 mm under a load of 750 g/cm² at50° C. for 16 hours, of 4 or more.
 4. The artificial leather basematerial according to claim 1, wherein, when a white polyurethane filmwith a thickness of 250 μm is pressure-bonded under heating to a surfaceof the artificial leather base material via a polyurethane adhesiveunder 5 Kg/cm² at 130° C. for 1 minute to form a resin layer-equippedartificial leather, and the resin layer-equipped artificial leather ispressurized under heating under 20 Kg/cm² at 150° C. for 1 minute, theartificial leather has a grade of color difference, determined in anevaluation of color migration to the white polyurethane film, of 3 ormore.
 5. The artificial leather base material according to claim 1,wherein the artificial leather base material has a grade of colordifference, determined in an evaluation of color migration using methylethyl ketone (MEK), of 2 or more.
 6. The artificial leather basematerial according to claim 1, wherein a product of a softness and athickness of the artificial leather base material is 2 or more.
 7. Theartificial leather base material according to claim 1, wherein theartificial leather base material comprises 0.5 to 20 parts by mass ofthe at least one cationic dye, per 100 parts by mass of the fiber basematerial.
 8. The artificial leather base material according to claim 1,wherein the artificial leather base material has a grade, determined ina water fastness test for a cotton cloth in accordance with JIS L 0846,of 4-5 or more.
 9. A resin layer-equipped artificial leather comprising:the artificial leather base material according to claim 1; and a resinlayer stacked on at least one surface of the artificial leather basematerial.
 10. The resin layer-equipped artificial leather according toclaim 9, wherein the resin layer has a surface with a lightness L* valueof >50.
 11. The resin layer-equipped artificial leather according toclaim 9, wherein a lightness difference ΔL* between the artificialleather base material and the resin layer is 10 or more.
 12. A nappedartificial leather obtained by napping at least one surface of theartificial leather base material according to claim 1, the artificialleather base material having a surface with a lightness L* value of ≤50.13. A shoe comprising: the napped artificial leather according to claim12 as an upper material; and an outsole bonded to the upper material,the outsole having a lightness L* value of >50.
 14. A decorating sheet,comprising: the artificial leather base material according to claim 1.15. The decorating sheet according to claim 14, wherein the decoratingsheet is a preform molded body shaped into a three-dimensional shape.16. A decorative molded body comprising: a molded body to be decorated;and the decorating sheet according to claim 14 that is stacked andintegrated on the molded body to be decorated.
 17. The decorative moldedbody according to claim 16, wherein the molded body to be decorated hasa lightness L* value of >50.
 18. The decorative molded body according toclaim 16, wherein a lightness difference ΔL* between the decoratingsheet and the molded body to be decorated is 10 or more.